Yellow to orange disazo cationic dyes containing two quaternary ammonium groups

ABSTRACT

Disclosed herein are biscationic disazo dyes and a process for dyeing nylon therewith at a pH of about 4 to 7. The dyes have good exhaust and buildup on acidmodified BCF nylon fibers as well as good light-fastness and wet fastness on such fibers. The dyes have the formula   WHEREIN X is selected from -CH2-, -C(CH3)2-, -NH-, -O-, -OCH2(CH2)1-2O-, -OCH2CH(OH)CH2O-, -SO2-, -S-, -S-S-, -NHCO-, and -NHCONH-; R1 is selected from H, CH3, C2H5, Cl, and Br; R2 is selected from H, alkyl, alkoxy, Cl, NHCO-alkyl, and NHCOC6H5; R3 is selected from H, alkyl, and alkoxy; Y is selected from   WHEREIN N IS 0 OR 1; Z is H when n is O and Z is OH when n is 1; Q is selected from NR4R5R6, and NHCOCH2NR4R5R6; R4 is selected from alkyl, and hydroxyalkyl; R5 is selected from alkyl, hydroxyalkyl, and cyclohexyl; R6 is selected from H, alkyl and benzyl; R4 and R5, optionally, can form an alicyclic ring, or a heterocyclic ring including the nitrogen atom or, together with R6, can form a pyridinium ring; A is an anion.

United States Patent 1 James 1 1 YELLOW TO ORANGE DISAZO CATIONIC DYES CONTAINING TWO QUATERNARY AMMONIUM GROUPS [75] Inventor:

[73] Assignee: E. I. du Pont de Nemours and C0., Wilmington, Del.

[22] Filed: Sept. 19, 1973 [21] Appl. No.3 398,575

Daniel Shaw James, Hockessin, Del.

alkyl 260/567.6 M [51] Int. C1..C09b 35/04; C0913 35/22; C091) 35/26 [58] Field of Search 260/174, 148, 177, 184, 260/175, 186, 129

[56] References Cited UNITED STATES PATENTS 2,945,849 7/1960 Kruckenberg et a1. 260/185 3,074,926 1/1963 Sartori .1 260/191 3,086,003 4/1963 Baumann ct a1. 260/146 R 3,133,910 5/1964 Baumann et a1 260/146 R 3,148,181 9/1964 Wallace et a1. 260/207 3,454,552 7/1969 Yamaya et a1. 260/155 3,532,683 10/1970 Sartori 260/207 3,542,758 11/1970 Hegar 260/156 3,649,162 3/1972 James 260/157 X 3,700,398 10/1972 Cole 8/21 E 3,759,893 9/1973 James 260/149 FOREIGN PATENTS OR APPLICATIONS 47-37675 9/1972 Japan 260/178 Primary Examiner-Floyd D. Higel Attorney, Agent, or Firm-James A. Costello [57] ABSTRACT Disclosed herein are biscationic disazo dyes and a process for dyeing nylon therewith at a pH of about 4 to 7. The dyes have good exhaust and buildup on acid- June 17, 1975 modified BCF nylon fibers as well as good lightfastness and wet fastness on such fibers. The dyes have the formula wherein R is selected from H, CH C H Cl, and Br;

R is selected from H, alkyl, alkoxy, C1,

NHCO-alkyl, and NHCOC H R is selected from H, alkyl, and alkoxy;

Y is selected from wherein n is 0 or 1;

Zis H whenn isOandZisOH when n is l;

Q is selected from NR R R and NHCOCH NR R R R is selected from alkyl, and hydroxyalkyl;

R is selected from alkyl, hydroxyalkyl, and

cyclohexyl;

R is selected from H, alkyl and benzyl;

R and R optionally, can form an alicyclic ring, or a heterocyclic ring including the nitrogen atom or, together with R can form a pyridinium ring;

A" is an anion.

17 Claims, N0 Drawings YELLOW TO ORANGE DISAZO CATIONIC DYES @ONTAHNKNG TWO QUATERNARY AMMONHUM GROUPS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention concerns biscationic, disazo dyes for dyeing acid-modified nylong styling yarns under neutral to weakly acidic conditions.

2. Description of the Prior Art With the introduction of acid-modified nylons the range of multicolored effects obtainable on bulk continuous filament BCF nylon styling carpeting has been increased. Acid-modified nylons, which contain sulfonic acid groups on the polymer chain, are dyeable with cationic dyes but have little or no affinity for acid dyes. Thus, a carpet containing two or three nylons of varying affinity for acid dyes (nonacid-modified nyions) and an acid-modified nylon that is not stained by acid dyes can be dyed at will with any combination of shades, including primary colors (those colors that cannot be obtained by combining other colors) side by side on the same carpet. Dyeing methods have been developed so that such carpets can be dyed with acid and cationic dyes in a single dyeing operation.

The following are among the most important considerations when choosing cationic dyes for the acid modified nylon fibers in nylon styling carpeting and these considerations are met by the novel dyes of this invention:

l. the dyes should have a high degree of lightfastness;

2. they should show a minimum of cross-staining on the unmodified nylon yarns; cross-staining causes dullness, a decrease in shade contrast between yarns of different colors and possibly a decrease in fastness properties;

3. they should have a high degree of wetfastness, to prevent cross-staining of the unmodified nylon yarns when the carpet is shampooed.

SUMMARY OF THE INVENTION The dyes of this invention have the formula alkyl N CH (|)H(Cl1 -Q;

wherein n is O or 1; Z is H when n is O and Z is OI-l when n is I; Q is selected from NR R R and NHCOCl-I NR R R R is selected from alkyl, and hydroxyalkyl;

R is selected from alkyl, hydroxyalkyl, and cyclohexyl;

R is selected from H, alkyl and benzyl;

R and R optionally, can form an alicyclic ring, or a heterocyclic ring including the nitrogen atom or, together with R can form a pyridinium ring;

A" is an anion.

Herein, the terms alkyl, alltoxy and hydroxyalkyl are meant to include such groups having from 1 to 4 carbon atoms.

In a process for dyeing nylon styling yarns containing acid-modified and unmodified nylon fibers comprising contacting said yarns with a dye dispersed in an aqueous dyebath having a pH of from 3 to 9, the improvement comprising employing a biscationic disazo dye of this invention at a pH of from about 4 to 7, whereby the unmodified nylon fibers are substantially unstained by the dye.

DETAILS OF THE INVENTION The novel dyes of this invention are prepared by conventional, art-known procedures. An aromatic diamine such as one of those listed in Table 1, having the gen eral structure X 0 Nil Y0 II (where R is H, alkyl, alkoxy, Cl, NHCOalkyl or NHCO- phenyl; R is H, alkyl or alkoxy; Y is -N\ alky l TABLE 1 Examples of Diamines Useful for Preparing Dyes of this lnvention 4,4-methylenedi(mtoluidine) 4,4'-methylenebis( Z-bromoaniline) 4,4-diaminodiphenylmethane 4,4-oxydianiline 4,4'-thioclianiline 4,4 '-sulfonylbis( Z-chloroaniline) 4,4'-sulfonyldi(o-toluidine) 4,4"dithiodi( m-toluidine) 4,4"dilhiobis( 3-chloroaniline) 4,4'-dithiodianiline 4,4-diaminodiphenylamine 4,4'-diaminodiphenyl sulfone 4,4'-diaminobe nzanilide N,N-bis(4-aminophenyl )urea 4,4'-thiobis( 2-chloroaniline) l,3-bis(4-aminophenoxy )-2- propanol N,N'-bis( 3ethyl-4-aminophenyl )urea l,3-bis(4-aminophenoxy propane l ,2-bis(4-aminophenoxy)ethane The coupling reaction can be carried out by dissolving the coupler in water at room temperature or below (preferably at 520C.) then slowly adding the tetrazonium salt preparation to it, or vice versa. To increase the reaction rate, the pH of the reaction mixture can be raised to about 3-4 by adding a suitable inorganic salt or base, such as an alkali metal acetate, carbonate, bicarbonate or hydroxide. The resulting dyes of this invention can be salted from solution, if necessary, and isolated by filtration.

Dyes in which the coupler is the salt of a tertiary amine, where R is H, can be used in that form or quaternized by any of the agents known for this purpose in the art. Common quaternizing agents include alkyl chlorides, bromides and iodides, benzyl chloride, bromide and sulfate, alkyl sulfates and alkyl p-toluenesulfonates.

For economic reasons, the preferred anion is chloride. However, substitution of other anions does not impair the desirable properties of the subject dyes and would only alter the solubility and the crystalline form of the dyes. Various procedures are available for introducing other anions. For instance, salts such as zinc chloride, sodium iodide or sodium fluoborate can be used as salting agents to precipitate the biscationic dyes or after dye formation, can be effected by any of the agents known in the art for this purpose; thus anions such as bromide, methosulfate or p-toluenesulfonate can be introduced.

The couplers containing a pendant tertiary or quaternized amine group are prepared by methods known in the art. For example, N-alkyl anilines, optionally substituted in the 2- and/or 5-positions, are

l. reacted with ethylene oxide, giving the N-(B- hydroxyethyl) derivatives. Replacement of the hydroxyl group with a halogen atom and subsequent addition of a secondary or tertiary amine gives pendant tertiary amine or quaternary ammonium salts, respectively,

2. reacted sequentially with ethyleneimine, chloroacetyl chloride and a secondary or tertiary amine, giving pendant tertiary amine or quaternary ammonium salts, respectively,

3. reacted sequentially with epichlorohydrin and a secondary or tertiary amine, or,

4. reacted with epichlorohydrin, then with ammonia to replace the terminal chlorine with a primary amine group, and then sequentially with chloroacetyl chloride and a secondary or tertiary aminev Other useful couplers are prepared by condensing chlorobenzene, optionally substituted in the 2- and/or 5-positions, with piperazine and alkylating or quaternizing with an alkyl halide or sulfate. Examples of couplers that are useful for preparing dyes of this invention are given in Table 2.

TABLE 2 Examples of Couplers Useful for Preparing Dyes of this Invention ci-i OCH H N 69 C,H,N(CH3),CH,CBH,

cm. can,

TABLE 2 Continued Examples of Couplers Useful for Preparing Dyes of this Invention 6 TABLE 2 Continued Examples of Couplers Useful for Preparing Dyes of this Invention The biscationic disazo dyes of this invention have good exhaust and buildup on acid-modified BCF nylon fibers. Polymers for such fibers are described, for instance, in US. Pat. No. 3,184,436, and contain sulfonate groups along the polymer chain which act as dye sites for basic or cationic dyes. In addition, the dyes have good to excellent fastness to light and exhibit an unexpectedly high degree of wetfastness on such fibers. The instant dyes display an almost total lack of affinity for unmodified nylon fibers under neutral to weakly acidic conditions. In other words, at pH 4-7, the biscationic dyes almost completely reserve nylon fibers which do not contain sulfonate groups. This behavior differs from that of known monocationic yellow dyes, which tend to stain unmodified nylon under nearneutral conditions and which display good reserve only under more acidic conditions of pH of 4 or below.

At neutral to weakly acidic conditions, pH 4-7, the subject cationic dyes can be applied to nylon styling carpet in conjunction with neutral-dyeing acid dyes,-

which have satisfactory exhaust and Ievelness under these conditions.

Commercial nylon styling carpet usually contains acid-modified nylon and from two to four unmodified nylons of varying acid dye receptivity which are tufted onto a backing in a random pattern to give the desired styling effects.

In order to evaluate cationic and acid dyes for this end-use, however, a test carpeting is used in which the various nylons are tufted onto a backing in discreet bands. The instant dyes were evaluated on a test carpet with the following specifications: Five bands of trilobal, jet-bulked BCF nylon yarns, spun from the nylon flake, are tufted onto a nonwoven polypropylene backing, each band being six tufts in width. The first band is acid-modified, 1300 denier BCF nylon (such as that described in US. Pat. No. 3,184,436). The other four bands are unmodified, 3700 denier BCF nylons which have progressively increasing acid dye receptivity by virtue of an increasing amine-end content, which ranges from to more than 100 gram-equivalents of free amine ends per grams of polymer. The specific amine-end range for each band is as follows:

1) 5-25 gram-equivalents light-dycable" with acid 2) 25-55 gram-equivalents iiitdium-dyeablc" with acid 3) 55-100 gram-equivalents ZiZ ep-dyeable" with acid 4) 100-120 gram-equivalents l t radeep-dyeable with acid dyes The deep-dyeing nylons (3) and (4) are disclosed in US. Pat No. 3,078,248.

The carpeting is dyed by the procedure used for commercial styling carpet, which can be dyed with acid and cationic dyes in the same dye bath by using as a dyeing assistant a sulfobetaine of the general structure (CH CH 0 0l'l Cl-l OH where R aliphatic hydrocarbon radical of 7-17 carbon atoms; in 03; p 0--3; and m +p 4. The preparation of these compounds is described in U.S. Pat. No. 3,280,179. The functions of the sulfobetaine additive are to prevent coprecipitation of the acid and cationic dyes, to enhance the levelness of both classes of dye without suppressing buildup and to minimize crossstaining.

The sulfobetaine dyeing assistant can be used in amounts as low as 0.05% of the weight of the fiber being dyed, but the best results are obtained with 02-03%. Amounts in excess of 0.5% of the weight of the fiber have led to an increase in cross-staining.

The dyes can be applied to nylon styling yarns by an exhaustion procedure, for instance in a heck, or by a pad-steam procedure, such as is used in continuous dyeing operations. The subject dyes can also be printed onto nylon styling carpeting, with excellent results.

Evaluation of the instant dyes was carried out by dyeing them singly onto nylon test carpeting in the absence of any acid dyes. In this way, the degree of crossstaining on the unmodified nylons is readily apparent. Staining occurs most readily on the unmodified band containing the least number of free amine ends, since this nylon contains the highest density of carboxylic acid end groups, which can act as dye sites for cationic dyes. Staining by cationic dyes can be induced on the deep-dyeable" and ultradeep-dyeable" nylons by 0 raising the dyeing pH, or by suitable choice of dye. However, the staining of the light-dyeable and "medium-dyeable bands would then be so bad as to be quite unacceptable. A reasonable candidate will barely stain the first two bands and will leave the higher amine end nylons untouched.

The biscationic dyes described hereinabove have significantly better nonstaining properties on unmodified nylon at pH 4-7 than any known commercial yellow to orange cationic dye.

A major deficiency of available commercial cationic dyes for use on acid-modified nylon in nylon styling yarns has been their tendency to bleed under certain conditions. For example, bleeding can occur when the styling yarn is subjected to shampooing or continual exposure to moisture. With high contrast styling yarn (e.g., carpeting) this results in a muddying effect or a staining of the light-dyeable component by dye bleeding from the heavy-dyed cationic dyeable component.

The properties of the subject dyes make them suit able for carpeting, upholstery, accent rugs, and even or apparel, where it is particularly important to employ dyes which have a high degree of wetfastness and resistance to bleeding.

The presence of an alkyl or alkoxy group in a position ortho (e.g., R to the azo linkage in the subject biscationic dyes results in increased pH sensitivity, causing a shade change to occur when dyeing under acidic conditions (e.g., dilute acetic acid). The shade change is readily reversible by treatment with dilute base (e.g., ammonium hydroxide). This phenomenon is, no doubt, attributable to the enhanced basicity of the azo linkage, which facilitates protonation thereon, caused by the effect of the electron releasing character of the ortho alkyl or alkoxy groups.

The preparation of the dyes of this invention are illustrated by the following Examples where parts are given by weight.

EXAMPLE 1 A stirred slurry of 50.1 parts of 4,4'-oxydianiline in 250 parts of water and 203 parts of 1ON-hydrochloric acid was cooled to 0-5C. and treated with 127 parts of SN-sodium nitrite solution. The resulting tetrazo compound dissolved completely in the reaction medium. Excess nitrite was destroyed with sulfamic acid.

Next, 353 parts of [3-(N-e thyl-m-toluidino)-2- hydroxypropyl]trimethylammonium chloride were added to the stirred tetrazo solution over a period of 5-10 minutes at 5-10C. The pH of the reaction mixture was then adjusted to 3 with parts of sodium acetate and parts of 30% caustic soda solution and the mixture was stirred at 5-10C. for 2% hours, the pH being kept at 3 by adding sodium acetate as necessary.

The mixture was heated to 35-40C. and 280 parts of isopropanol were added, followed by a solution of parts of sodium fluoborate in 200 parts of water. The pH was raised to 4 with 30% caustic soda solution, after which the dye began to crystallize from solution. The mixture was stirred at 40C. for V2 hour and then cooled to room temperature and stirred overnight. The solids were separated by filtration, washed with 600 parts of 1% sodium fluoborate solution and then with 200 parts of water, slurried in 1,000 parts of isopropanol for 40 minutes, isolated by filtration, washed with 800 parts of isopropanol and dried. A yield of 194 parts ofa yellow solid was obtained, m.p. l 68C. A visi- 9 I ble spectrum of the dye in dimethylacetamide/acetic Mm1- lacid (3/1) showed a peak (A,,,,,, at 435 my. and a b Based on the above procedure, the structure of the sorptivity (a thereat of 78.7 l.g. emf. y is C 3 --.r-":.r tmom. 1W2: N 2

6 C H *(Cl I 2 1 3 2 EXAMPLE 3 Found: C, 55.7; H. 6.6; N, 12.0; 1120 N, 6.1 Cale for CHHMBZFKNKOS, C. 5m; H e 125; azo N, 61 4,4-Methylened1an1lme hydrochloride (6.8 parts) was tetrazotized by a procedure similar to that described in Example 1. The tetrazo preparation was then added to a solution of 16.3 parts of [Z-(N-ethyl-mtoluidino)-ethy1carbamoylmethyl]trimethylammonium chloride in 120 parts of water, the temperature of which was 5l0C. and the pH of which had been ad- Based on the above procedure and analysis, the justed with acetic acid to 5-5.5. The reaction rnass bestructure of the dye is came quite syrupy and crystallized after a few more CF3 OH 2 EXAMPLE 2 4 grams of sodium fluoborate had been added. The mixture was stirred overnight at room temperature and the N,N-bis(4-aminopheny1)urea 10.2 parts) was diazsolids were then isolated by filtration, washed with waotized by a procedure similar to that of Example 1. The ter, reslurried in water, isolated by filtration and dried. tetrazonium salt preparation was treated with sulfamic Yield: 20.5 parts. In dimethylacetamide/water (4:1), acid to destroy excess nitrite and then clarified by filthe dye had a 64.0 1.g. cm. at k 431 mu. tration through Hiflo Supercell. To the clarified solu- Based on the above procedure, the structure of the tion were then added 21.5 parts of [2-(N-ethylanilino) dye is ethylltrimethylammonium chloride, the reaction mix- The dyes f the f ll i Examples 4 to 31 were ture being maintained at -1000 The P was adjusted pared by procedures similar to those of Examples l3. to and maintained at With Sodium acetate for 2 Using these same procedures one skilled in the art will hours. The dye gradually crystallized from the reaction be l to employ a tetrazonium salt f a diamine f m which W218 then stirred Overnight at room p 50 Table 1 with a coupler of Table 2 to make useful disazo ature. Thirty parts of sodium chloride were added and dyes f this invention, f which Examples 1 to 31 are the solids were isolated by filtration, washed with representative parts of 10% salt solution and then with 40 parts of isoh dyes f Examples 4 5 7 9 1 1 13 and 15 to 31 propanol, and dried, yielding 21.0 parts of reddishh h f l brown powder. In dimethylacetamide/water (4/1), the The dyes of Examples 6, 8, l0, l2 and 14 have the dye had an absorptivity (11 of 78.9 Lgf'cmf' at formula R C H .1 2 X l 1 1 l=N N 2A f CH -CH-CH -Q R e m. Amax. Shade On Acid- Example X R, R; --Q A (l.g.cm.") (my) Modified Nylon Q 4 CHZ- H N(CH;,);, 65.8 435 Yellow Q 5 CH CH3 N(CH5)2CH3 62.0 420 Yellow 6 cH cH -N(CH BB9 71.2 432 Golden Yellow Q 7 CH2 CH3 H N(CH3)3 BEG 22.9 395 Tan Yellow Q s -CH2 CH3. H N(CH on 430 Gold Yellow 9 cH,- CH3 CH N(C2H5)2CH3 5 425 Gold Yellow 10 cH, cH cH N(CH3)3 BB9 432 Gold Yellow Q ll CH2 cl H mcHoe BB9 52.9 435 Gold Yellow Q l2 -cH, Cl cH 'N(Ch on 64.4 463 Orange Q l3 o- H H -N(CH3)3 ZnCh 61.8 419 Yellow Q 14 -o H H -N(CH- ZnCl 70.5 450 Yellow Q l5 -o- H CH3 NHCOCH2N(CH3)3 BB9 59.8 455 Gold Yellow Q 16 o H CH3 -N(CH5)2CH3 0 60.3 422 Yellow Q 17 -s0 H H N(CH3)3 on 64.9 458 Red Yellow Q 18 -0- H H --N(C,H,,)3 znclfi 63.0 420 Yellow Q 19 CH2 H H --N(C2H5)3 zncl. 52.0 420 Yellow Q 20 cH, H H N(CH3)2CH2C5H5 on 54.0 4l5 Yellow Q 21 -0- H H -N(CH;.)2CH2C6H5 01 64.0 420 Yellow 3 22 0 H H (9 cl 46.5 425 Gold Yellow -N(C 3l2 CH3 23 o H 'H C1 45.5 420 Yellow (9 Q 9 24 0 H H -N c H.oH) c,H Cl 58.7 420 Yellow (3 25 o- H H znclfi 58.9 420 Yellow CH 3 e 26 so- H H CI 53.0 460 Gold Yellow -NeH CH3 27 -s- H H 2mm. 67.0 440 Gold Yellow Q e 28 s s H H O znclF 700 430 Gold Yellow 0 g; a 29 H H N(CH,OH)C2H5 ZnClfi 48.2 425 Gold Yellow NHCNH- q; 30 OCH,C|HCH,O- H H -N(C Ho)o zoclfi' 45.0 4l0 Yellow OH 9 Q 31 -OCHCH2CH,O- H H -N(CH3) 1 CI 49.8 410 Yellow UTILITY EXAMPLES the absence of acid dyes.

EXAMPLE 32 Dyeing of Banded BCF Nylon Carpeting 21. Bleach Scour cationic dyes on unmodified nylon, they were dyed in 100 Parts of the carpeting described above were heated for minutes at 80F. in 4000 parts of water containing sodium perborate 4 parts trisodium phosphate 025 part a sulfobetaine* 0.5 part CH CH OH 69/ 9 R-H-CH CH CH S0 I CH CH OH where R C alkyl (-30%), C alkyl (-30%) and C monounsaturated (-40%). The temperature was raised to 160F. for minutes and the carpet rinsed in water at 100F.

b. Dyeing Procedure The carpeting was added to 4000 parts of water containing the aforementioned sulfohetaine 1 part the tetrasodium salt of ethylenediamine tetraacetic acid 025 part tetrasodium pyrophosphatc 0.2 part EXAMPLE 33 Continuous Dyeing of Nylon Styling Carpeting Using Kusters Equipment as described in Textile Chemist and Colorist" Jan. 14, 1970, pp. 6-12, nylon styling carpeting containing acid-modified, mediumdyeable and ultradeep-dyeable nylons tufted in a random pattern on a nonwoven polypropylene backing was run through a wet-out bath at 80F. containing an organic alcohol extended with ethylene oxide 15 g/l a sulfated polyglycol ether 0.6 g/l Pickup was about 80%. The carpeting was then 5 g/l continuously treated with an aqueous dye bath composition containing the dye of Example 18 an organic alcohol extended with ethylene oxide 0.25 g/l a sulfated polyglycol ether 1.25 g/l a purified natural gum ether 2 g/l the sulfobetaine described in Example 32 5 g/l acetic acid 3 g/l monosodium phosphate to adjust pH to about 5 The dye bath temperature was 80F. Pickup was about 200%. The carpeting was then run through a steamer at 212F., in which the dwell time was 8 minutes. The carpeting was rinsed thoroughly and dried. The acidmodified nylon fibers were dyed a deep yellow shade; the unmodified fibers were negligibly stained.

EXAMPLE 34 Printing of BCF Nylon Styling Carpet A sample of nylon styling carpet containing acidmodified, medium-dyeable and ultradeep-dyeable nylons tufted in a random pattern on a nonwoven polypropylene backing was printed with a mixture containing the cationic dye of Example 13 5 parts the sulfobetaine described in Example 32 0.5 part glacial acetic acid 5 parts Carregeenin thickener to give the desired viscosity Water to I00 parts The carpeting was steamed at 2l2220F. for 10 minutes, rinsed, scoured for 15 minutes at F. in a 0.03% aqueous solution of the condensation product of 20 moles of ethylene oxide with 1 mole ofC alcohol,

rinsed and dried. The acid-modified nylon fibers were dyed a deep yellow shade; the unmodified fibers had a negligible stain.

EXAMPLE 35 Evaluation of Wetfastness Samples of banded nylon carpeting were dyed (on an equal strength basis), according to the procedure described in Example 32, with a. the dyes of Examples 13 and 18, and

b. a commercially available cationic yellow, C.I.

Basic Yellow 45, having the structure and disclosed in US. Pat. No. 3,435,022 as having good wetfastness on polyacrylonitrile fibers.

The amount of bleed and stain onto the lightdyeable end of the nylon styling carpet was evaluated for each of the above dyes as follows:

A 6 X 6 inch square of the dyed carpet was treated with 25 ml. of a hard water test solution consisting of 2 parts of magnesium sulfate, 2 parts of calcium chloride and 1892 parts of distilled water. The carpet was then air dried for 24 hours. The resultant stain on the light-dyeable nylon component was rated using the American Association of Textile Chemists and Colorists Chart for Measuring Transference of Color using a rating scale of from 1 to 5 with the numbers having the following significance:

5 negligible or no stain 4 slightly stained 3 noticeably stained 2 considerably stained 1 heavily stained The above steps were repeated until the rating of the stain was equal to 4 or less.

The aforementioned treatment procedure was re peated using 25 ml. of a 30 g/l solution of a commercially available anionic detergent. Results are given in Table 3. They show the superior wetfastness properties of the subject biscationic dyes over the commercial monocationic dye.

TABLE 3 Number of Runs X (Staining on Light-Dyeable" The embodiments of the invention in which an exclusive property or priviledge is claimed are defined as follows:

l. A dye having the formula ZisH whenn isO andZis OH when n is l; Q is selected from NR R R and NHCOCH NR R R R is selected from alkyl, and hydroxyalkyl;

R is selected from alkyl, hydroxyalkyl, and cyclohexyl;

R is selected from H, alkyl and benzyl;

R and R form an alicyclic ring;

A is an anion; the alkyl, alkoxy, NHCOalkyl and hyl0 droxyalkyl substituents refer to such substituents havand NHCONH; R, is selected from H, CH C H Cl, and Br;

R is selected from H, alkyl, alkoxy, Cl, NHCO-alkyl,

and

R is selected from H, alkyl, and alkoxy;

nisOorl;

c2115 0 n=n n g cu -sag ing 1 to 4 carbon atoms.

2. A dye according to claim 1 wherein Y is,

and wherein Q, Z and n are as defined in claim 1.

3. A dye according to claim 2,

4. A dye according to claim 3, wherein A is BF; 5. A dye according to claim 2,

6. A dye according to claim 5,

7. A dye according to claim 6 wherein 2A is ZnCL, 8. A dye according to claim 5,

en m -M0119 1 O CH CH -L (c 11 2A 9. A dye according to claim 8 wherein 2A is ZnClf. 13. A dye according to claim 12, wherein 2A is 10. A dye according to claim 5, ZnClf.

11. A dye according to claim 10 wherein A is Cl. 14. A dye according to claim 2,

12. A dye according to claim 2, 15. A dye according to claim 14 wherein 2A is Oil ZnClf.

16. A dye according to claim 2, 

1. A DYE HAVINT THE FORMULA
 2. A dye according to claim 1 wherein Y is,
 3. A dye according to claim 2,
 4. A dye according to claim 3, wherein A is BF4 .
 5. A dye according to claim 2,
 6. A dye according to claim 5,
 7. A dye according to claim 6 wherein 2A is ZnCl4 .
 8. A dye according to claim 5,
 9. A dye according to claim 8 wherein 2A is ZnCl4 .
 10. A dye according to claim 5,
 11. A dye according to claim 10 wherein A is Cl .
 12. A dye according to claim 2,
 13. A dye according to claim 12, wherein 2A is ZnCl4 .
 14. A dye according to claim 2,
 15. A dye according to claim 14 wherein 2A is ZnCl4 .
 16. A dye according to claim 2,
 17. A dye according to claim 16 wherein A is Cl . 